Process for increasing the reactivity of naturally or artificially shaped articles or materials and product obtained thereby



Patented Sept. 27, 1938 UNITE PATENT OFFICE PROCESS FOR INCREASING THE REACTIV- ITY OF NATURALLY R ARTIFICIALLY SHAPED ARTICLES OR MATERIALS AND PRODUCT OBTAINED THEREBY tion of Germany No Drawing. Application September 12, 1935,

Serial No. 40,352. 1934 9 Claims.

My present invention relates to a process for -increasing the reactivity of naturally or artificially shaped articles.

One of its objects is to provide a increasing the reactivity ficially shaped articles. Another object is the provision of structured proteinous materials having an increased affinity for treating agents of acid character. Further objects will be seen from the detailed specification following hereinafter. 1

This invention is based on the observation that artificially or naturally shaped articles or materials, which consist of or contain protein substances, their derivatives or substitution products, for example wool, chlorinated wool or wool pretreated with hydrogen peroxide, loaded or not loaded natural silk, artificial silk from flbroin, pelts, feathers, horsehair, horn, hardened or not hardened casein, gelatin sheets or capsules, tanned or raw hides, may be treated, if desired after the finishing process with alkylene oxide or a derivative or analogue or isologue thereof with retention of their structure so as to produce therein conversion products having an enhanced reactivity, particularly towards treatment with substances containing acid groups which may also have been converted into salt groups.

ample, acylating agents, acid dyestuffs, natural or artificial tanningagentsi acid mordants, acid loading agents, acid resists,iacid insecticides.

The invention consists in the treatment of such shaped articles or materials with an alkylene- 5 oxide, for example, ethylene-oxide, propyleneoxide, cyclohexene-oxide, epichlorhydrin, glycide, phenoxy-propenoxide, glycidic acids and their salts, salts of propylene-oxide sulfonic acid, 8-hydro-oxyquinoline-glycide-ether, ethylene- 4o lmine, N-methylethylene-imine, piperidopropenoxide, tri-ethyloxidopropyl-ammonium-chloride, furthermore alkylene sulfides, such as 1.2-propylene sulfide, and l-chloro-2.3-propylene sulfide.

The ethylene-oxide body may be applied to the goods in the form of a solution in water or an organic solvent, or in the form of gas and at ordinary or raised temperature, under normal, diminished or increased pressure. When treating the material with a. gas the efllciency of the action depends not only on the amount of vapor present in the mixture of air and vapor, in which form the treatment is preferably carried out, but also on the proportion of the amount of material, for instance wool to be treated, to the volume of the gaseous medium. When the proportion process for of naturally or arti- Such acid treating agents are, for ex- In Germany September 15,

of wool to the volume of a mixtureof eplchlorhydrine vapor and air is 1:100 the quantity of epichlorhydrine may be 10 to 30 per cent calculated on the quantity of wool. When changing the aforesaid proportion of wool and gaseous mixture to 1:50 the upper limit of epichlorhydrine is reduced to about 25 per cent. With butylene oxide which is of slower reaction, a higher concentration is necessary for a. useful effect. The proportions just given all refer to a treatment of the material for 8 to 16 hours at a temperature of 40 to 66 C. and a content of to of relative moisture in the air. The treatment may be localized by printing with a thickening agent which contains a slightly volatile or non-volatile ethylene-oxide or the salt of a glycidic acid or the like. The reaction may be carried without the use of a catalyst. However, the reaction may be promoted by a catalyst such as an amine, for instance, triethylamine, diethylaniline, isopropylaniline, salts of a water soluble and even diiiicultly soluble base with an acid capable of reacting with alkylene oxides, for instance, sodium acetate, sodium chloride, calcium chloride, ammonlumchloride, tetramethylammoniumchloride, dodecyltrlmethylammoniumchloride. Small quantities of amine, for instance, 1 to 5 per cent triethylamine are already sufiicient. It is also recommended, that at the beginning 'of the operation the medium should be slightly acid. For example the material may be wetted with dilute acetic acid. In the course of the reaction the acidity is consumed. There may also be present in the reaction a swelling agent, for instance, formamide, acetamide, thiourea, phenol, resorcinol, salicylic acid, sodium salicylate, potassium thlocyanate, sodium cresol sulfonate, furthermore oxidizing or reducing bleaching agents or known preserving agents against deleterious influence of alkali.

The enhanced affinity for acid dyestufis is particularly important in the case of wool. It permits the use of a lower temperature in dyeing mixtures of wool with acetate artificial silk, which is not stable to boiling, without diminishing the exhaustion of the dyestufl; or the diminution of the addition of acid-to top dyeing, so that a direct dyeing acetate dyestufi which is only moderately fast to top dyeing is less superficially adsorbed by the wool or silk and purer two-color efiects faster to rubbing are produced. Also in dyeing or topping haifwool in a neutral Glaubers salt bath with acid dyestuffs theimprovement of the afiinity oi the wool is of importance.

- noticeable as a falling-oil the wet tenacity.

The increase of the affimty for acid agents corresponds with a diminution of the affinity for basic substances if there is no acid residue introduced together with or during the treatment. One obtains, therefore, on wool or natural silk,

which has been treated with propylene-oxide or preferably epichlorhydrin for example, dyeings of diminished depth with basic dyestufis such as Methyl-Violet. This strengthening oi the basic properties becomes even more marked when the treating agent contains basic nitrogen, for instance when piperido-propenoxide is used.

By combination of treated and untreated material valuable variegated efl'ects can be obtained, for example, powerful mixed tints can beproduced in which the difference in depth 01 tint may be varied by varying the temperature of dyeing or the proportion of acid added or both. By topping or grounding with basic dyestuifs or by the simultaneous use of more than one acid dyestuif of relatively different aflfinity to the treated and untreated material two-color efiects may be obtained. Obviously the treatment is not limited to individual materials; mixed fibers, for instance, mixed yarn oi acetate artificial silk and wool, mixed yarn of viscose staple fiber and wool. mixed fabrics, garments which are to be re-dyed and old material may equally well betreated according to the invention.

On treating keratin products with allqlene oxides of relatively low molecular weight, for instance, with propylene oxide or epichlorhydrine, the substitution can proceed until the molecule of keratin has been charged with 0.17 radicals of alkylene oxide on one atomic proportion of nitrogen. In this reaction there may be introduced into the amino groups of the material, for instance, the omega amino group 01' the lysine radical more than one hydroxyalkyl group. Thisreaction may proceed to the formation of quaternary salt groups. Correspondingly the products do no longer produce a reaction with triketohydrindene. The hydroxyallql groups can be identified by acetylation with acetic anhydride and determination of the bound acetyl groups.

It may remain an unanswered question" whether and to what degree other groups than basic groups ahe modified or substituted.

The following examples illustrate the invention:

Example 1.--Zephyr wool is treated in a liquor ratio of 1:40 for 8 hours at 40 C. with a solution of propylene-oxide in water of 1 per cent strength. The wool, apart from quite :light yellowing, is apparently unchanged, further it exhibits, particularly in neutral or acid dyebaths, an essentially stronger. afiinity to acid dyestuffs, for instance, Alizarine Direct Blue A (Schultz Farbstoiftabellen, 7th edition, vol. 2, page 9), than does a comparative sample which has been similarly treated with water alone. If 2 per cent of triethyiamine calculated on the quantity of wpol is added to the propylene-oxide solution with which the wool is treated the dyeings are still deeper. The afiinity to basic dyestuffs, for instance, Methyl Violet, is diminished to a corresponding extent. The treated wool is instance cardings, the known dyeing apparatus may be used for the treatment.

Example 2.The same wool as is prescribed in Example 1 (1 part by weight) is heated to C. in a moist condition for 8 hours in the vapor of propylene-oxide part). It now behaves towards dyestuffs similarly to that of the treated material prescribed in Example 1. In like manner yarn material, for example woolen crepe sliver, may be improved the dry and wet tenacity is not varied by the action of the propyleneoxide.

Example 3.--Loaded and not loaded natural silk are heated as described in Example 2 for 8 hours in a chamber at 40 C. containing air laden with ethylene-oxide. In both cases the aflinity of the treated silk for acid dyestufis, for instance, Eosin S (Schultz Farbstofitabellen, 7th edition, vol. 1, No. 883), A20 Wool Blue (Schultz Farbstofitabellen, 7th edition, vol. 1, No. 103) and Alizarine Direct Blue A (Schultz Farbstofitabeh len, 7th edition, vol. 2, page 9) is notably increased. Externally the silk remains unchanged.

Emmple 4.--Woolen piece goods are saturated with a solution or 10 per cent strength of glycide in water and then centrifuged. The impregnated material is not externally changed by being heated at 40 C. for9 hours but has acquired a considerably increased affinity for and dyestuffs.

Example 5.Horn' shavings are heated for 10 hours in a closed vessel at 60 C. with an aqueous solution of 10 per cent strength of propyleneoxide. The drained and dried shavings can be dyed with Alizarine Direct Blue A more deeply than a sample of the original horn which has been heated with water alone.

Example -6.--Alum-tanned leather is suspended in moist condition for 8 hours in air containing ethylene oxide and at 50 C. The treated leather is dyed by means oi said dyestuiis more intensely than that which has not been treated.

Example 7.-A mixed yarn containing about 50% of wool and 50%0! artificial fibers from viscose'cut into staples are stored for 16 hours at 40 C. in air containing vapor of propylene oxide. When dyeing this yarn-in 1% solution of Pegubrown (Schultz Farbstofltabellen, 1th edition,

vol. 2, page 1'13) the fiber thus treated is, dyed a darker shade already at 50-to 85 C. and shows a more uniform coloring than the untreated material.

Example 8.-Press-moulded plates made of the condensation product of casein and formaldehyde are immersed for 10 hours at 30 C. in an aqueous solution of 10 per cent strength of propylene-oxide. Even after thorough washing the treated plates can be dyed with acid dyestufls essentially more intensely than the like plates which have been immersed in water only at 30 C. for the same period.

Example 9.A ladys dress material made from a' yarn containing a mixture of 50 per cent of wool and 50 per cent 01' viscose fibers cut into staples, is impregnated at room temperature with a 10 per cent solution of the spirocyclic quaternary ammonium salt obtained from chlorohydroxy propyl piperidine by rearrangement, after 20 Example 10.-Wool yarn is treated at room temperature with a preferably freshly prepared about 10 per cent solution oi. 1.2-:propyleneoxide- 3-sulfonic-potassium obtainable by the addition of the equimolecular quantityoi potassium hydroxide to a solution of gamma-chloro-beta-hydIOXY-IJIOIJELIlB-a-SlllfOi'llC potassium for 20 minutes, centrifuged and heated to 40 C. for about 12 hours. The affinity to acid dyes is diminished owing to the presence of a sulfo group the aflinity to basic dyes, for instance Methyl-Violet (Schultz Farbstofitabellen, 7th edition, vol. 1, No. 783) is considerably increased. .The wool thus treated shows an increased capability for being wetted and can be dyed a deep shade at a relatively low temperature.

These facts show that in treating the wool according to the invention a substitution by chemical reaction occurs and not only a physical change of the surface.

A similar but smaller efiect is obtained if the propyleneoxide sulfonic potassium is replaced by glycidic acid potassium.

Example 11.-A degummed natural silk is treated in the same manner as has been described in Example 10 for treating wool. The result as to-the dyeing properties is the same. The afllnity to acid dyes is reduced and the ailinity to basic dyes is increased.

Example 12.-Wool yarn is thoroughly wetted with water containing small quantities of a wetting agent, thoroughly centrifuged and for 12 hours exposed to the action of a mixture. of epichlorhydrine vapor and air at a temperature of 40 C., the quantity of epichlorhydrine amounting to 20% of that of the wool and the vessel in which the reaction is carried out having 50 parts by volume ascompared with that of the applied wool. The aifinity of the treated wool for dyes or dyestufi components containing acid groups, for instance, Alizarine Direct Blue A, Thiazine Red R or Indigosol Green IBA (Schultz Farbstofftabellen, 7th edition, suppl. vol. 1, page 109 is extraordinarily increased. A similar, but not so strong efiect is obtained if the dry wool is treated with a mixture of epichlorhydrine vapor and air containing 75% of relative moisture under the same conditions. It must be assumed that the primary product of reaction is changed further by intramolecular alkylation. i

Example 13.-Wool is impregnated with a 5 per cent solution of piperidopropenoxideacetate,

centrifuged and heated for 16 hours to 40 C. The afiinity to dyestufis is considerably increased. A still stronger effect is obtained byapplication of the free base, but the strong alkaline reaction is mostly not desired. Instead of the piperldopropenoxideacetate there may also be used the prod-- Orange 2, (Schultz Farbstofftabellen both components of the not of addition from dimethylsulfate and piperidopropenoxide. i

Example 14.--A fiber mixture of two thirds of glossy acetate silk cut into staples and one third of wool is treated at 50 to 20 C. with a finely dispersed melt of olein containing about 50% o! epichlorhydrine calculated on the quantity of olein. The fiber mass obtained by removing the excess of olein and still containing 10 per cent of olein is kept in closed vessels for 12 hours at a temperature of 60 C. Hereafter the material is worked up in the usual manner. There is obtained a yarn which in spite of its low content of wool which shows good blending effects and uses up the dye very well at a temperature at which the acetate silk is not attacked.

Example 15.--Wool is treated with a 3 per cent solution of 1-N-perhydrocarbazolyl-2.S-propemoxideacetate at 40 to 50 C. and then heated at 50 to 55 C. for 16 hours. The aflinity to said dyes is increased.

Example 16.-Zephyr wool yarn is treated with a 3 per cent solution of l-dodecylmethylamino- 2.3-propenoxide-hydrochloride at 50 C. and is heated to 50 C. for 16 hours alter having been centrifuged. Acid dyes dye the material a darker tint, and there is obtained a softening eflect which stands washing.

The term "protein material" used in the claims is intended to include naturally orartificially.

shaped articles or materials consisting of or containing protein substances or derivatives or con-' version products thereof.

By the expression "structured proteinous masilk, fibroin artificial silk, pelts, feathers, horsehair, horn, casein-containing materials, gelatine sheets or capsules, tanned or raw hides and the like, as opposed to solutions or dispersions of protein substances.

What I claim is:

1. A process for increasing the reactivity of a structured protein material towards treating agents of acid character which comprises subjecting the material to the action of an alkylating agent selected from the group consisting of alkylene oxides, alkylene imines and alkylene sulfides under conditions not involving a change of structure of the parent material, whereby there is produced a water-insoluble proteinous article of the same physical form as said parent material.

2. A process for increasing the reactivity of a structured protein material towards treating agents of acid character which comprises subjecting the material to the action of an alkylating agent in gaseous condition selected from the group consisting of alkylene oxides, alkylene structure of the parent material, whereby there is produced a water-insoluble proteinous article of the same physical form as said parent material-in the presence of a catalyst.

4. A process for increasing the reactivity of a structured protein material towards treating agents of acid character which comprises sub- Jecting the material to the action of an alkyiating agent selected from the group consisting of alkylene oxides, alkylene imines and alkylene sulfides under conditions not involving a change of structure of the parent material, whereby there is produced a water-insoluble proteinous article oi the same physical form as said parent material in a slightly acid medium at the beginning of the reaction.

5. A process for increasing the reactivity 01' a structured protein material towards treating agents of acid character which comprises subjecting the material to the action of 1.2-a1kyleneimines under conditions not involving a change of structure of the parent material, whereby there is produced a water-insoluble proteinous article of the same physical form as said parent material.

6. A structured water-insoluble proteinous material consisting partly or wholly of keratine and 8. A structured textile material insoluble in acid aqueous liquids, said structured textile material consisting partially or wholly of keratine containing in its molecule hydroxyalkyl groups, said hydroxyalkylated keratine material being characterized over similarly structured but nonhydroxyaikylated keratine material by an enhanced reactivity towards dyestuffs containing acid groups.

9. A wool product having the same structural characteristics as naturally occurring wool, the wool product being characterized over natural wool by an enhanced reactivity towards dyestufis containing acid groups and by containing in its molecule hydroxyalkyl groups.

PAUL SCI-ILACK. 

